EP1813983B1 - Ébauche de masque de déphasage, masque de déphasage, et procédé de transfert de motif - Google Patents

Ébauche de masque de déphasage, masque de déphasage, et procédé de transfert de motif Download PDF

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Publication number
EP1813983B1
EP1813983B1 EP20070008067 EP07008067A EP1813983B1 EP 1813983 B1 EP1813983 B1 EP 1813983B1 EP 20070008067 EP20070008067 EP 20070008067 EP 07008067 A EP07008067 A EP 07008067A EP 1813983 B1 EP1813983 B1 EP 1813983B1
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EP
European Patent Office
Prior art keywords
phase shift
halftone phase
layer
light
film
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EP20070008067
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German (de)
English (en)
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EP1813983A3 (fr
EP1813983A2 (fr
Inventor
Hiroki Yoshikawa
Toshinobu Ishihara
Satoshi Okazaki
Yukio Inazuki
Tadashi Saga
Kimihiro Okada
Masahide Iwakata
Takashi Haraguchi
Mikio Takagi
Yuichi Fukushima
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Shin Etsu Chemical Co Ltd
Toppan Inc
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Shin Etsu Chemical Co Ltd
Toppan Printing Co Ltd
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Priority claimed from JP2004102388A external-priority patent/JP4535240B2/ja
Priority claimed from JP2004102427A external-priority patent/JP4535241B2/ja
Priority claimed from JP2004102219A external-priority patent/JP4348536B2/ja
Application filed by Shin Etsu Chemical Co Ltd, Toppan Printing Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Publication of EP1813983A2 publication Critical patent/EP1813983A2/fr
Publication of EP1813983A3 publication Critical patent/EP1813983A3/fr
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    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
    • A44B15/00—Key-rings
    • A44B15/005—Fobs
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; Preparation thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31616—Next to polyester [e.g., alkyd]

Definitions

  • This invention relates to a halftone phase shift mask for use in the photolithographic fabrication of semiconductor integrated circuits or the like and effective for phase shifting and attenuation of exposure light. More particularly, it relates to a halftone phase shift mask blank, a halftone phase shift mask obtained therefrom, and a pattern transfer method using the mask.
  • Photomasks are used in a wide variety of applications including the fabrication of semiconductor integrated circuits such as ICs, LSIs and VLSIs.
  • the photomask is prepared from a photomask blank having a chromium based light-shielding film on a transparent substrate, by forming a predetermined pattern in the light-shielding film by photolithography using UV or electron beams.
  • the current demand for a higher level of integration in the semiconductor integrated circuit market has created a need for a smaller feature size.
  • the traditional solutions are by reducing the wavelength of exposure light and increasing the numerical aperture of lens.
  • phase shift method A phase shift mask is used as a mask for transferring a micro-pattern.
  • a phase shift mask specifically a halftone phase shift mask is illustrated as comprising a substrate 1 and a phase shifter film 2 deposited thereon.
  • the mask consists of a phase shifter 2a that forms a pattern on the substrate and an uncovered area la of the substrate 1 that is exposed where the phase shifter 2a is absent.
  • a phase difference of about 180° is set between the light transmitted by the uncovered substrate area la and the light transmitted by the phase shifter 2a. Due to light interference at the pattern boundary, the light intensity at the interfering boundary becomes zero, improving the contrast of a transferred image.
  • the phase shift method permits to increase the focal depth for acquiring the desired resolution. This achieves improvements in resolution and exposure process margin, as compared with conventional masks having ordinary light-shielding patterns in the form of chromium film.
  • phase shift masks are generally divided for practical application into full transmission type phase shift masks and halftone type phase shift masks.
  • the full transmission type phase shift masks are transparent to the exposure light wavelength because the light transmittance of the phase shifter section is equal to the light transmittance of uncovered substrate areas.
  • the halftone type phase shift masks the light transmittance of the phase shifter section is several percents to several tens of percents of the light transmittance of uncovered substrate areas.
  • phase shift film 2 including a metal thin film 3 for controlling transmittance and a transparent film 4 having a sufficient thickness to induce a 180° phase shift to the light transmitted thereby is formed on a transparent substrate 1.
  • one known single-layer halftone phase shift mask has a phase shift film 2 (or semi-transmissive film 5) of MoSi base materials such as MoSiO or MoSiON (see JP-A 7-140635 ).
  • the single-layer halftone phase shift mask is an effective means for accomplishing a high resolution in a simple manner.
  • the light used for exposure becomes of shorter wavelength, a problem arises in mask defect inspection or the like.
  • Oxynitride films of metal and silicon having a relatively high oxygen or nitrogen content are commonly used as the semi-transmissive film 5 of single-layer halftone phase shift mask blank. They have the nature that their transmittance becomes higher as the wavelength of irradiating light becomes longer.
  • the resulting mask must be inspected for defects.
  • the defect inspection system uses light having a longer wavelength than that of a light source for exposure used in the lithography through that mask.
  • the defect inspection system generally uses a wavelength of near 260 nm, typically 266 nm, which is longer than the exposure wavelength 193 nm.
  • the halftone phase shifter has a considerably high transmittance to the inspection wavelength, preventing defect inspection at a sufficient precision.
  • the problem arising from the difference between inspection wavelength and exposure wavelength is noticed not only in terms of transmittance, but also in terms of reflectance.
  • a halftone phase shift film it is then desired for a halftone phase shift film to have minimal dependence of transmittance and reflectance on wavelength.
  • One solution to this problem is to construct the halftone phase shift film to a multilayer structure, specifically a halftone phase shift film 2 of the structure in which a film 7 having a phase shift function (typically a silicon oxide and/or nitride film containing a metal) is combined with a metal film 6 having a light absorbing function, as shown in FIG. 4 (see JP-A 7-168343 ).
  • a film 7 having a phase shift function typically a silicon oxide and/or nitride film containing a metal
  • Such a halftone phase shift mask is manufactured from a blank comprising a metal film, a phase shift film and a light-shielding film on a transparent substrate, by forming a photoresist film on the blank, patterning the photoresist film, and dry etching the light-shielding film through the resist pattern for transferring the pattern to the light-shielding film.
  • a dry etching technique using a chlorine-based gas is often selected at this etching stage since the light-shielding film is typically formed of a chromium-based material. Then, using the mask pattern transferred to the resist and the light-shielding film as an etching mask, dry etching is performed for transferring the pattern to the phase shift film.
  • phase shift film is typically formed of a metal-containing silicon oxide and/or nitride. Subsequent etching is performed on the metal film, completing the pattern transfer to all the layers of the halftone phase shift film. If the etching away of the metal film, which largely affects transmittance, is insufficient, it is impossible to manufacture a mask as designed. On the other hand, an attempt to remove the metal film completely often forces etching into the transparent substrate, which fails to provide a phase difference as designed and hence, a phase shift effect as expected.
  • an etch-susceptible material As the metal film, it is preferred to select an etch-susceptible material as the metal film. However, since the metal film is considerably thin, a choice of an extremely etch-susceptible material may allow the etching of the phase shift film to give damages to the substrate past the metal film. Since the transparent substrate used generally has a relatively high etching rate with respect to the fluorine-based gas used for the etching of the phase shift film, it can be readily damaged if over-etching occurs such that the metal film is completely removed during the etching of the phase shift film.
  • the pattern size of semiconductor integrated circuits becomes finer and finer.
  • the lithographic light source of a stepper (stepping projection aligner) or scanner for transferring the mask pattern to wafers has undergone a transition to a shorter wavelength region than KrF excimer laser (248 nm) and ArF excimer laser (193 nm), with the use of F 2 laser (157 nm) being under investigation.
  • phase shift masks are currently on predominant use as the photomask capable of reducing the pattern size.
  • research works are being made to develop a phase shift mask capable of accommodating exposure light of shorter wavelength.
  • phase shift masks especially halftone phase shift masks that shift the phase of exposure light transmitted by and attenuate the exposure light transmitted by, the constituent elements, composition, film thickness, layer arrangement and the like of the phase shift film must be selected such as to provide a desired phase difference and transmittance at the short wavelength of exposure light used, for example, the wavelength (157 nm) of F 2 laser.
  • some halftone phase shift films for F 2 laser (157 nm) exposure gain a transmittance at the exposure wavelength by resorting to a technique of providing a higher degree of oxidation, such as by increasing the content of oxygen in a film beyond the oxygen level in conventional halftone phase shift films for the ArF excimer laser exposure.
  • halftone phase shift films of MoSi system suffer from the problem that the resistance of oxide film to chemical liquid, especially alkaline liquid is unsatisfactory.
  • a preferred aim herein is to provide a halftone phase shift mask blank comprising a halftone phase shift film that satisfies a phase difference and transmittance upon exposure to shorter wavelength light, typically F 2 laser (157 nm) and that fully clears at a practical level the characteristics required in an overall process from the manufacture of a halftone phase shift mask to the pattern transfer using the mask, such as etching behavior, etching rate, conductivity (sheet resistance), chemical resistance and transmittance at the inspection wavelength; a phase shift mask prepared therefrom; and a pattern transferring method.
  • shorter wavelength light typically F 2 laser (157 nm)
  • the preferred aim may also be attained when the halftone phase shift film has a multilayer structure including in alternate formation at least one light-shielding layer for mainly adjusting transmittance and at least one transparent layer for mainly adjusting phase difference, with the outermost surface layer being a transparent layer, and the light-shielding layer, preferably both the light-shielding layer and the transparent layer, comprises silicon, a first metal component of molybdenum, and a second metal component of zirconium or hafnium or both, as constituent elements.
  • the resulting halftone phase shift mask blank satisfies a phase difference and transmittance upon exposure to shorter wavelength light, typically F 2 laser (157 nm) and fully clears at a practical level the characteristics required in an overall process from the manufacture of a halftone phase shift mask to the pattern transfer using the mask, such as etching behavior, etching rate, conductivity (sheet resistance), chemical resistance and transmittance at the inspection wavelength.
  • a halftone phase shift mask is obtained which is effective in a lithographic process involving exposure to short wavelength light, typically F 2 laser (157 nm).
  • An aspect of the present invention that addresses the preferred aim provides a phase shift mask blank, a phase shift mask and a pattern transferring method, as defined below.
  • the halftone phase shift mask blanks and halftone phase shift masks of the above aspect satisfies a phase difference and transmittance upon exposure to shorter wavelength light, typically F 2 laser (157 nm) and fully clears at a practical level the characteristics required in an overall process from the manufacture of a halftone phase shift mask to the pattern transfer using the mask, such as etching behavior, etching rate, conductivity (sheet resistance), chemical resistance and transmittance at the inspection wavelength.
  • the masks enable effective pattern exposure using short wavelength light, typically F 2 laser (157 nm).
  • the intermediate layer in a structure including a substrate, an intermediate layer lying on the substrate and a top layer lying on the intermediate layer, the intermediate layer includes an upper region disposed adjacent the top layer and a lower region disposed adjacent the substrate. Also the intermediate layer has a lower side (or surface) disposed adjacent the substrate and an upper side (or surface) disposed remote from the substrate, which are referred to as “substrate side” and “remote side,” respectively.
  • substrate side or surface disposed adjacent the substrate and an upper side (or surface) disposed remote from the substrate
  • halftone phase shift mask blanks halftone phase shift masks and pattern transfer methods in embodiments of the present invention that attain the preferred aim.
  • the halftone phase shift mask blank of the preferred embodiment comprises a substrate which is transparent to exposure light and a halftone phase shift film formed thereon having a preselected phase difference and transmittance.
  • the halftone phase shift film has a multilayer structure including in alternate formation at least one light-shielding layer for mainly adjusting transmittance and at least one transparent layer for mainly adjusting phase difference, with the outermost surface layer being a transparent layer.
  • the light-shielding layer preferably both the light-shielding layer and the transparent layer, comprise silicon, a first metal component of molybdenum, and a second metal component of zirconium or hafnium or both, as constituent elements.
  • the halftone phase shift mask blank of this embodiment comprises a substrate of quartz (synthetic quartz) which is transparent to exposure light, especially exposure light of short wavelength such as F 2 laser (157 nm).
  • a halftone phase shift film having a multilayer structure including at least one light-shielding layer for mainly adjusting transmittance and at least one transparent layer for mainly adjusting phase difference is formed on the substrate. The layers are alternately arranged such that the outermost surface layer is a transparent layer.
  • a halftone phase shift mask blank comprising a halftone phase shift film composed of two layers, one light-shielding layer and one transparent layer is illustrated in FIG. 6 .
  • a light-shielding layer 621 and a transparent layer 622 are laid in order to form a halftone phase shift film 62.
  • each layer have both a function of adjusting phase difference and a function of adjusting transmittance.
  • the phase difference and transmittance of respective layers are adjusted such that the overall halftone phase shift film (all the layers of halftone phase shift film) may have desired values of phase difference and transmittance.
  • the light-shielding layer and the transparent layer are different in transmittance.
  • the transparent layer has a higher transmittance than the light-shielding layer.
  • the light-shielding layer preferably both the light-shielding layer and the transparent layer, comprise silicon, a first metal component of molybdenum, and a second metal component of zirconium or hafnium or both, as constituent elements.
  • the content of silicon is at least 90 atom%, preferably at least 95 atom%, based on the total of silicon and first and second metal components.
  • the upper limit of silicon content is preferably up to 99 atom%.
  • the halftone phase shift film may have a lower etching rate, especially a lower rate of etching with fluorine-based gas and become less processable.
  • the layer comprising silicon and first and second metal components and hence, the entire halftone phase shift film including that layer may have a lower electroconductivity or an increased sheet resistance, which can invite dielectric breakdown or cause a charge build-up to SEM for line width measurement.
  • the layer of which the halftone phase shift film is constructed preferably has a sheet resistance of up to 1 ⁇ 10 12 ohm/square.
  • the layers of the halftone phase shift film are laid up such that the rate of etching with fluorine-based gas of the respective layers may increase from the substrate side toward the remote side and the rate of etching with chlorine-based gas of the respective layers may decrease from the substrate side toward the remote side.
  • the layers of the halftone phase shift film are laid up such that the conductivity of the respective layers may decrease from the substrate side toward the remote side.
  • the light-shielding layer and preferably both the light-shielding layer and the transparent layer comprises silicon, a first metal component of molybdenum, and a second metal component of zirconium or hafnium or both.
  • the preferred layer comprising silicon and first and second metal components encompasses a layer containing two elements: Mo and Zr; a layer containing two elements: Mo and Hf; and a layer containing three elements: Mo, Zr and Hf as the metal elements.
  • the atomic ratio of first metal component to second metal component [M1/M2] is preferably up to 5. If the atomic ratio of first metal component to second metal component is more than 5, the layer may become less resistant to chemical liquid, especially alkaline cleaning liquid such as APM.
  • the preferred contents of silicon and first and second metal components are such that the content of silicon is 90 to 99 atom%, the content of first metal component is up to 8.3 atom%, and the content of second metal component is at least 0.15 atom%, based on the total of silicon and first and second metal components [Si+M1+M2].
  • the total of silicon and first and second metal components is 100 atom%.
  • the atomic ratio of the first metal component to the second metal component [M1/M2] is preferably up to 6. If the atomic ratio of first metal component to second metal component is more than 6, the layer may become less resistant to chemical liquid, especially alkaline cleaning liquid such as APM.
  • the preferred contents of silicon and first and second metal components are such that the content of silicon is 95 to 99 atom%, the content of first metal component is up to 4.3 atom%, and the content of second metal component is at least 0.15 atom%, based on the total of silicon and first and second metal components [Si+M1+M2].
  • the total of silicon and first and second metal components is 100 atom%.
  • the layer comprising silicon and first and second metal components may further comprise at least one light element selected from the group consisting of hydrogen, oxygen, nitrogen, carbon and halogen, as a constituent element, and more preferably oxygen or nitrogen or both.
  • Illustrative are compounds containing silicon and first and second metal components, for example, oxides such as MoZrSiO (if the first and second metals are Mo and Zr) or MoHfSiO (if the first and second metals are Mo and Hf); nitrides such as MoZrSiN (if the first and second metals are Mo and Zr) or MoHfSiN (if the first and second metals are Mo and Hf); and oxynitrides such as MoZrSiON (if the first and second metals are Mo and Zr) or MoHfSiON (if the first and second metals are Mo and Hf).
  • the layers are preferably laid up such that the atomic ratio of the sum of first and second metal components to silicon, [(M1+M2)/Si], decreases from the substrate side toward the remote side.
  • each layer further comprises a light element component (L) of oxygen or nitrogen or both
  • the layers are preferably laid up such that the atomic ratio of the light element component to the sum of silicon, first and second metal components, and light element component, [L/(Si+M1+M2+L)], increases from the substrate side toward the remote side.
  • the system for inspecting defects in the halftone phase shift film uses light having a longer wavelength than that of exposure light used in the lithography.
  • the film often has a higher transmittance at the inspection wavelength.
  • the halftone phase shift film adapted thereto has so high a transmittance at the inspection wavelength, for example, a wavelength of about 257 nm, as to inhibit inspection.
  • the halftone phase shift film is composed of multiple layers which are constructed as mentioned above, the light reflected by a layer on the remote side interferes with the light reflected by a layer on the substrate side to reduce the transmittance at the inspection wavelength used in the inspection of the halftone phase shift film, for example, a wavelength of about 257 nm. Then a distinct contrast relative to the quartz is so readily established that the inspection of the halftone phase shift film is facilitated.
  • the wavelength at which the halftone phase shift film exhibits a lower transmittance can be selected by properly adjusting the composition and thickness of the halftone phase shift film.
  • the thickness of the halftone phase shift film necessary to provide a preselected phase difference and transmittance is reduced, the dimensional accuracy of dry etching is improved. This is because the phase difference is also affected by interference.
  • This embodiment is effective for reducing the influence of interference and thus allows the halftone phase shift film to be designed to a reduced thickness.
  • a layer having a higher conductivity may be laid on the substrate side, minimizing the risks of dielectric breakdown and a charge build-up in SEM for line width measurement. There are advantages including a good contrast upon line width measurement by SEM and ease of pattern repair.
  • the layers of the halftone phase shift film be laid up such that the extinction coefficient of respective layers decreases from the substrate side toward the remote side.
  • the thickness of layers of the halftone phase shift film is not particularly limited.
  • the light-shielding layer preferably has a thickness of 1 to 30 nm, more preferably 5 to 20 nm, and the transparent layer preferably has a thickness of 50 to 120 nm, more preferably 40 to 70 nm.
  • the entire halftone phase shift film has a thickness of about 70 to 150 nm, especially about 70 to 90 nm.
  • the halftone phase shift film of such a halftone phase shift mask blank may be deposited by selecting any of metal targets, silicon targets and metal and silicon-containing targets in accordance with the composition of the light-shielding or transparent layer, feeding an inert gas such as helium, neon or argon gas into the chamber, and sputtering the target.
  • an inert gas such as helium, neon or argon gas
  • the first and second metals are molybdenum and zirconium
  • a choice is made among a neat molybdenum target, a neat zirconium target, a neat silicon target, a sintered target of molybdenum and zirconium, a sintered target of molybdenum and silicon, a sintered target of zirconium and silicon, and a sintered target of molybdenum, zirconium and silicon.
  • the targets are combined so that the layer deposited therefrom may contain Si, Mo and Zr in a desired proportion.
  • first and second metals are molybdenum and hafnium
  • a choice is made among a neat molybdenum target, a neat hafnium target, a neat silicon target, a sintered target of molybdenum and hafnium, a sintered target of molybdenum and silicon, a sintered target of hafnium and silicon, and a sintered target of molybdenum, hafnium and silicon.
  • the targets are combined so that the layer deposited therefrom may contain Si, Mo and Hf in a desired proportion.
  • first and second metals are Mo, Zr and Hf
  • the targets are combined so that the layer deposited therefrom may contain Si, Mo, Zr and Hf in a desired proportion.
  • the sputtering may be performed by selecting one or more from the foregoing targets.
  • the process is a multiple simultaneous sputtering, known as co-sputtering.
  • the layer of the halftone phase shift film is formed of a compound comprising silicon and first and second metal components such as an oxide, nitride or oxynitride
  • it may be deposited by reactive sputtering using a mixture of an inert gas and a reactive gas such as oxygen-containing gas or nitrogen-containing gas, typically nitrogen, oxygen or nitrogen oxide gas.
  • reactive sputtering is performed by using a target consisting of molybdenum, zirconium and silicon, or a target consisting of molybdenum and silicon and a target consisting of zirconium and silicon, and optionally a neat silicon target and mixing argon gas as an inert gas with nitrogen gas and oxygen gas as reactive gases.
  • the sputtering technique is not particularly limited although DC sputtering is typically employed.
  • the composition of the halftone phase shift film contains components originating from the target or targets, that is, silicon and first and second metal components.
  • the contents of respective components can be tailored by altering the composition of the target containing plural elements, or by controlling the electric powers applied to a plurality of targets if used.
  • the power applied to each target is preferably about 100 to 1,000 watts, more preferably about 200 to 900 watts, thought not limited thereto.
  • the content of a component originating from the reactive gas typically a light element component such as oxygen or nitrogen can be tailored by properly controlling the amount of the reactive gas (e.g., oxygen- or nitrogen-containing gas) fed to the sputtering chamber and optionally the amount of the inert gas fed.
  • a component originating from the reactive gas typically a light element component such as oxygen or nitrogen
  • the reactive gas e.g., oxygen- or nitrogen-containing gas
  • the halftone phase shift film on the surface is oxidized in air, it changes its composition and thickness with the passage of time and accordingly changes its phase difference and transmittance. If the halftone phase shift film is previously oxidized to such an extent that no further oxidation proceeds in a normal environment, the influence of oxidation in air on phase difference and transmittance is avoided. Specifically, the halftone phase shift film is heated in an oxygen-containing atmosphere, typically air, thereby forming a thermally oxidized thin film on the surface (the surface of outermost layer). Equivalent results are obtained when any of oven heating, lamp annealing and laser heating is used as the heating means.
  • the phase shift mask is manufactured by patterning the halftone phase shift film on the halftone phase shift mask blank of the preferred embodiment as produced above. More specifically, by patterning the halftone phase shift film 62 (consisting of light-shielding layer 621 and transparent layer 622 lying on the substrate in order) on the phase shift mask blank shown in FIG. 6 , a phase shift mask as shown in FIG. 7 is manufactured.
  • the phase shift mask includes patterned translucent regions 62a and transparent regions 61a therebetween.
  • the phase shift mask of the structure shown in FIG. 7 may be manufactured by a process as shown in FIG. 8 .
  • a halftone phase shift film 62 (consisting of orderly lying linht-shidding layer 621 and transparent layer 622) is formed on a transparent substrate 61 by the process described above, a resist film 63 is coated on the film 62 ( FIG. 8A ).
  • the resist film 63 is patterned by lithography including electron beam exposure and development ( FIG. 8B ), after which the phase shift film 62 is dry etched ( FIG. 8C ), and the resist film 63 is subsequently stripped ( FIG. 8D ).
  • application of the resist film, patterning (exposure and development), etching, and removal of the resist film may be carried out by known methods.
  • etching with a fluorine-based gas such as fluorocarbon, e.g., C 2 F 6 , CF 4 , C 3 F 8 or SF 6 or etching with a chlorine-based gas such as Cl 2 .
  • a fluorine-based gas such as fluorocarbon, e.g., C 2 F 6 , CF 4 , C 3 F 8 or SF 6
  • etching with a chlorine-based gas such as Cl 2 .
  • Etching with a fluorine-based gas is advantageous because of a higher etching rate.
  • the halftone phase shift masks of the preferred embodiment are advantageously used in the imagewise exposure of photoresists involved in the fabrication of semiconductor integrated circuits.
  • the exposure wavelength with which the halftone phase shift mask blanks and halftone phase shift masks of this embodiment are operable is not particularly limited. Any exposure wavelength such as KrF excimer laser (248 nm), ArF excimer laser (193 nm) and F 2 laser (157 nm) is applicable. Particularly when the F 2 laser (157 nm) is used as the exposure wavelength, the halftone phase shift mask blanks and halftone phase shift masks (halftone phase shift films) of the preferred embodiment fully meet the required characteristics.
  • Examples 1-13 and Experiments 1-2 relate to preferred embodiments of the invention.
  • a halftone phase shift mask blank was obtained by depositing a halftone phase shift film of two layers on a synthetic quartz substrate of 6 inch square which was fully transparent to F 2 laser light (wavelength 157 nm).
  • a DC sputtering system For the deposition of a halftone phase shift film, a DC sputtering system was used. By disposing a mix target containing molybdenum, zirconium and silicon in a molar ratio Mo:Zr:Si of 5:1:20 (Mo 5 Zr 1 Si 20 target) and a silicon (Si) target and inducing binary co-sputtering, a halftone phase shift film was deposited.
  • first layer a light-shielding layer
  • second layer a transparent layer
  • a reactive gas was fed to the chamber along with an inert gas to carry out reactive sputtering, depositing the halftone phase shift film.
  • the thickness of the light-shielding (first) layer and the transparent (second) layer was determined such that the overall halftone phase shift film had a transmittance of 6% and a phase difference of 180° at the F 2 laser wavelength (157 nm), while the influence of a thermally oxidized thin film to be formed on the transparent (second) layer was taken into account.
  • the thickness of the light-shielding (first) layer was 86 ⁇
  • the thickness of the transparent (second) layer was 649 ⁇
  • the thickness of the overall halftone phase shift film was 735 ⁇ .
  • the halftone phase shift film thus produced was analyzed. Its spectral transmittance data are shown in Table 1. The results of composition analysis by ESCA are shown in Table 2. The transmittance near 250 nm is suppressed low due to the interference between the reflected lights from the light-shielding (first) layer and the transparent (second) layer.
  • compositional ratios of Si, Mo and Zr in the light-shielding (first) layer and the transparent (second) layer of the halftone phase shift film were computed from the results of composition analysis.
  • compositional ratios of O and N relative to the total constituent elements in the light-shielding (first) layer and the transparent (second) layer were computed.
  • the light-shielding (first) layer and the transparent (second) layer were separately deposited as a single layer. Each layer was measured for sheet resistance. Also the etching rate of each layer was measured by dry etching with fluorine-based gas or chlorine-based gas under the conditions shown below. The results are shown in Table 3. The extinction coefficient of each layer at 157 nm is also shown in Table 3.
  • halftone phase shift mask blank obtained by depositing the light-shielding (first) layer and the transparent (second) layer according to the above procedure was heat treated in an oven at 300°C.
  • a resist material was coated onto the halftone phase shift mask blank, exposed to electron beams, and developed with a developer, forming a resist pattern.
  • a resist pattern By dry etching through the resist pattern as a protective film, the halftone phase shift film of the halftone phase shift mask blank was patterned. The dry etching was under the fluorine-based gas conditions. This resulted in a halftone phase shift mask having a satisfactory halftone phase shift film pattern.
  • a halftone phase shift mask blank was obtained by depositing a halftone phase shift film of two layers on a synthetic quartz substrate of 6 inch square which was fully transparent to F 2 laser light (wavelength 157 nm).
  • a DC sputtering system For the deposition of a halftone phase shift film, a DC sputtering system was used. By disposing a mix target containing molybdenum, zirconium and silicon in a molar ratio Mo:Zr:Si of 5:1:20 (MO 5 Zr 1 Si 20 target) and a silicon (Si) target and inducing binary co-sputtering, a halftone phase shift film was deposited.
  • first layer a light-shielding layer
  • second layer a transparent layer
  • a reactive gas was fed to the chamber along with an inert gas to carry out reactive sputtering, depositing the halftone phase shift film.
  • the thickness of the light-shielding (first) layer and the transparent (second) layer was determined such that the overall halftone phase shift film had a transmittance of 6% and a phase difference of 180° at the F 2 laser wavelength (157 nm), while the influence of a thermally oxidized thin film to be formed on the transparent (second) layer was taken into account.
  • the thickness of the light-shielding (first) layer was 64 ⁇
  • the thickness of the transparent (second) layer was 698 ⁇
  • the thickness of the overall halftone phase shift film was 762 ⁇ .
  • the halftone phase shift film thus produced was analyzed. Its spectral transmittance data are shown in Table 4. The results of composition analysis by ESCA are shown in Table 5. The transmittance near 250 nm is suppressed low due to the interference between the reflected lights from the light-shielding (first) layer and the transparent (second) layer.
  • Table 4 Phase difference (deg) Transmittance (%) Film thickness ( ⁇ ) 157 nm 157 nm 193 nm 257 nm 266 nm 179.1 6.01 24.45 35.78 37.76 762
  • Table 5 O N Mo Zr Si 1st layer (at%) 1.8 15.1 3.9 0.8 78.4 2nd layer (at%) 47.4 15.5 1.3 0.3 35.5
  • compositional ratios of Si, Mo and Zr in the light-shielding (first) layer and the transparent (second) layer of the halftone phase shift film were computed from the results of composition analysis.
  • compositional ratios of O and N relative to the total constituent elements in the light-shielding (first) layer and the transparent (second) layer were computed.
  • the halftone phase shift mask blank obtained by depositing the light-shielding (first) layer and the transparent (second) layer according to the above procedure was heat treated as in Example 1.
  • Example 2 a resist pattern was formed on the halftone phase shift mask blank, and the halftone phase shift film was then patterned by dry etching under the fluorine-based gas conditions. This resulted in a halftone phase shift mask having a satisfactory halftone phase shift film pattern.
  • a halftone phase shift mask blank having a halftone phase shift film containing a proportion (shown in Table 7) of silicon and metal was dry etched under the following conditions. An etching rate was determined and calculated based on an etching rate of 1 for the film having a silicon proportion of 67 atom%. Dry etching
  • a halftone phase shift film was deposited on a synthetic quartz substrate of 6 inch square which was fully transparent to F 2 laser light (wavelength 157 nm).
  • a DC sputtering system was used.
  • Two targets were used in a combination of a mix target containing molybdenum and silicon in a molar ratio Mo:Si of 1:9 (Mo 1 Si 9 target) and another mix target containing zirconium and silicon in a molar ratio Zr:Si of 1:9 (Zr 1 Si 9 target) or a combination of a mix target containing molybdenum, zirconium and silicon in a molar ratio Mo:Zr:Si of 5:1:20 (MO 5 Zr 1 Si 20 target) and a silicon (Si) target.
  • Binary co-sputtering was carried out while applying properly controlled powers across the targets.
  • a reactive gas which was oxygen gas or a mixture of nitrogen and oxygen gases was fed into the chamber at a flow rate as shown in Tables 8 and 9.
  • a halftone phase shift film was deposited. In this way, halftone phase shift films of varying compositions were deposited to produce a series of halftone phase shift mask blanks.
  • the sheet resistance of the mask blanks is also shown in Tables 8 and 9.
  • Table 8 Silicon proportion Mo/Zr Gas flow rate (SCCM) Sheet resistance ( ⁇ /cm 2 ) Ar N 2 O 2 90% 1 40 - 1-2 1.0 ⁇ 10 5 -3.0 ⁇ 10 5 95% 1 40 - 1-2 1.0 ⁇ 10 6 -5.0x10 7 99% 1 40 - 1-2 1.0 ⁇ 10 7 -1.0x10 1 100% - 40 - 1-2 5.0 ⁇ 10 11 -1.0x10 13
  • a halftone phase shift mask blank was obtained by depositing a halftone phase shift film of two layers on a synthetic quartz substrate of 6 inch square which was fully transparent to F 2 laser light (wavelength 157 nm).
  • a DC sputtering system For the deposition of a halftone phase shift film, a DC sputtering system was used. In Examples 3 to 7, binary co-sputtering was carried out using two targets: a mix target containing molybdenum and silicon in a molar ratio Mo:Si of 1:9 (Mo 1 Si 9 target) and another mix target containing zirconium and silicon in a molar ratio Zr:Si of 1:9 (Zr 1 Si 9 target).
  • binary co-sputtering was carried out using three targets: a mix target containing molybdenum and silicon in a molar ratio Mo:Si of 1:9 (Mo 1 Si 9 target), another mix target containing zirconium and silicon in a molar ratio Zr:Si of 1:9 (Zr 1 Si 9 target), and a silicon target.
  • first layer a light-shielding layer
  • second layer a transparent layer
  • a reactive gas was fed to the chamber along with an inert gas to carry out reactive sputtering, depositing the halftone phase shift film.
  • the thickness of the light-shielding (first) layer and the transparent (second) layer was determined such that the overall halftone phase shift film had a transmittance of 6% and a phase difference of 180° at the F 2 laser wavelength (157 nm).
  • the thickness of the overall halftone phase shift film is shown in Table 10.
  • an atomic ratio Mo/Zr ⁇ 5 ensures a change of phase difference of less than 3.0 degrees and a change of transmittance of less than 0.5% in the alkaline cleaning liquid test.
  • the contents of Mo and Zr that satisfy an atomic ratio Mo/Zr ⁇ 5 are Mo ⁇ 8.3 atom% and Zr ⁇ 1.7 atom% for the silicon proportion of 90 atom%; and Mo ⁇ 0.83 atom% and Zr ⁇ 0.17 atom% for the silicon proportion of 99 atom%.
  • an atomic ratio Mo/Zr ⁇ 6 ensures a change of phase difference of less than 3.0 degrees and a change of transmittance of less than 0.5% in the alkaline cleaning liquid test.
  • the contents of Mo and Zr that satisfy an atomic ratio Mo/Zr ⁇ 6 are Mo ⁇ 4.3 atom% and Zr ⁇ 0.7 atom% for the silicon proportion of 95 atom%; and Mo ⁇ 0.85 atom% and Zr ⁇ 0.15 atom% for the silicon proportion of 99 atom%.
  • a halftone phase shift mask blank was obtained by depositing a halftone phase shift film of two layers on a synthetic quartz substrate of 6 inch square which was fully transparent to F 2 laser light (wavelength 157 nm).
  • a DC sputtering system was used for the deposition of a halftone phase shift film.
  • binary co-sputtering was carried out using two targets: a mix target containing molybdenum, and silicon in a molar ratio Mo:Si of 1:9 (Mo 1 Si 9 target) and another mix target containing zirconium and silicon in a molar ratio Zr:Si of 1:9 (Zr 1 Si 9 target).
  • sputtering was carried out using a silicon target.
  • first layer a light-shielding layer
  • second layer a transparent layer
  • a reactive gas was fed to the chamber along with an inert gas to carry out reactive sputtering, depositing the halftone phase shift film.
  • the thickness of the light-shielding (first) layer and the transparent (second) layer was determined such that the overall halftone phase shift film had a transmittance of 6% and a phase difference of 180° at the F 2 laser wavelength (157 nm). Specifically, the thickness of the light-shielding (first) layer was 75 ⁇ , the thickness of the transparent (second) layer was 648 ⁇ , and the thickness of the overall halftone phase shift film was 723 ⁇ .
  • the halftone phase shift film thus produced was analyzed. Its spectral transmittance data are shown in FIG. 9 and Table 13. As seen from FIG. 9 , the transmittance near 250 nm is suppressed low due to the interference between the reflected lights from the light-shielding (first) layer and the transparent (second) layer. Table 13 Phase difference (deg) Transmittance (%) Film thickness ( ⁇ ) 157 nm 157 nm 193 nm 257 nm 266 nm 175.3 6.01 34.2 32.5 36.0 723
  • compositional ratios of Si, Mo and Zr in the light-shielding (first) layer of the halftone phase shift film were approximately estimated below.
  • the halftone phase shift mask blank obtained by depositing the light-shielding (first) layer and the transparent (second) layer according to the above procedure was heat treated as in Example 1.
  • Example 2 a resist pattern was formed on the halftone phase shift mask blank, and the halftone phase shift film was then patterned by dry etching under the fluorine-based gas conditions. This resulted in a halftone phase shift mask having a satisfactory halftone phase shift film pattern.
  • a halftone phase shift mask blank was obtained by depositing a halftone phase shift film of two layers on a synthetic quartz substrate of 6 inch square which was fully transparent to F 2 laser light (wavelength 157 nm).
  • a DC sputtering system was used for the deposition of a halftone phase shift film.
  • binary co-sputtering was carried out using two targets: a mix target containing molybdenum, zirconium and silicon in a molar ratio Mo: Zr:Si of 5:1:20 (Mo 5 Zr 1 Si 20 target) and a silicon target.
  • sputtering was carried out using a silicon target.
  • first layer a light-shielding layer
  • second layer a transparent layer
  • a reactive gas was fed to the chamber along with an inert gas to carry out reactive sputtering, depositing the halftone phase shift film.
  • the thickness of the light-shielding (first) layer and the transparent (second) layer was determined such that the overall halftone phase shift film had a transmittance of 6% and a phase difference of 180° at the F 2 laser wavelength (157 nm), while the influence of a thermally oxidized thin film to be formed on the transparent (second) layer was taken into account.
  • the thickness of the light-shielding (first) layer was 98 ⁇
  • the thickness of the transparent (second) layer was 651 ⁇
  • the thickness of the overall halftone phase shift film was 749 ⁇ .
  • the spectral transmittance data of the halftone phase shift film are shown in Table 14.
  • Table 14 Phase difference (deg) Transmittance (%) Film thickness ( ⁇ ) 157 nm 157 nm 193 nm 257 nm 266 nm 176.9 6.01 32.65 31.57 32.58 749
  • Table 15 O N Mo Zr Si 1st layer (at%) 32.9 13.4 2.8 0.6 50.3 2nd layer (at%) 25.3 24.6 - - 50.1
  • compositional ratios of Si, Mo and Zr in the light-shielding (first) layer of the halftone phase shift film were computed from the results of composition analysis.
  • compositional ratios of O and N relative to the total constituent elements in the light-shielding (first) layer and the transparent (second) layer were computed.
  • the halftone phase shift mask blank obtained by depositing the light-shielding (first) layer and the transparent (second) layer according to the above procedure was heat treated as in Example 1.
  • Example 2 a resist pattern was formed on the halftone phase shift mask blank, and the halftone phase shift film was then patterned by dry etching under the fluorine-based gas conditions. This resulted in a halftone phase shift mask having a satisfactory halftone phase shift film pattern.
  • a halftone phase shift mask blank was obtained by depositing a halftone phase shift film of two layers on a synthetic quartz substrate of 6 inch square which was fully transparent to F 2 laser light (wavelength 157 nm).
  • a DC sputtering system For the deposition of a halftone phase shift film, a DC sputtering system was used. Binary co-sputtering was carried out on two targets: a mix target containing molybdenum, hafnium and silicon in a molar ratio Mo:Hf:Si of 5:1:20 (Mo 5 Hf 1 Si 20 target) and a silicon target, depositing a halftone phase shift film.
  • first layer a light-shielding layer
  • second layer a transparent layer
  • a reactive gas was fed to the chamber along with an inert gas to carry out reactive sputtering, depositing the halftone phase shift film.
  • the thickness of the light-shielding (first) layer and the transparent (second) layer was determined such that the overall halftone phase shift film had a transmittance of 6% and a phase difference of 180° at the F 2 laser wavelength (157 nm). Specifically, the thickness of the light-shielding (first) layer was 82 ⁇ , the thickness of the transparent (second) layer was 637 ⁇ , and the thickness of the overall halftone phase shift film was 719 ⁇ .
  • Table 17 The spectral transmittance data of the halftone phase shift film are shown in Table 17.
  • Table 18 Phase difference (deg) Transmittance (%) Film thickness ( ⁇ ) 157 nm 157 nm 193 nm 257 nm 266 nm 178.2 6.04 26.56 35.53 37.74 719
  • Table 18 O N Mo Hf Si 1st layer (at%) 1.8 15.1 3.9 0.8 78.4 2nd layer (at%) 42.5 15.1 0.4 0.1 35.3
  • compositional ratios of Si, Mo and Hf in the light-shielding (first) layer and the transparent (second) layer of the halftone phase shift film were computed from the results of composition analysis.
  • compositional ratios of O and N relative to the total constituent elements in the light-shielding (first) layer and the transparent (second) layer were computed.
  • the halftone phase shift mask blank obtained by depositing the light-shielding (first) layer and the transparent (second) layer according to the above procedure was heat treated as in Example 1.
  • Example 2 a resist pattern was formed on the halftone phase shift mask blank, and the halftone phase shift film was then patterned by dry etching under the fluorine-based gas conditions. This resulted in a halftone phase shift mask having a satisfactory halftone phase shift film pattern.

Claims (13)

  1. Ebauche de masque de déphasage comprenant
    - un substrat (61) qui est transparent à la lumière d'exposition et
    - un film de déphasage (62) sur celui-ci ayant une différence de phase et transmittance présélectionnées, caractérisée en ce que
    ledit film de déphasage possède une structure multicouche comportant, selon une formation alternative, au moins une couche de protection contre la lumière (621), essentiellement pour ajuster la transmittance et au moins une couche transparente (622), essentiellement pour ajuster la différence de phase, une couche de surface extérieure du film étant une couche transparente précitée,
    ladite couche de protection contre la lumière comprend du silicium, un premier composant métallique M1 constitué de molybdène, et un deuxième composant métallique M2 constitué de zircone ou d'hafnium ou des deux, comme éléments constituants.
  2. Ebauche de masque de déphasage selon la revendication 1, dans lequel ladite au moins une couche transparente comprend du silicium, le premier composant métallique M1 et le deuxième composant métallique M2 comme éléments constituants.
  3. Ebauche de masque de déphasage selon la revendication 2, dans laquelle le rapport atomique de la somme des premier et deuxième composants métalliques au silicium [(M1+M2)/Si] diminue depuis le côté du substrat vers le côté éloigné.
  4. Ebauche de masque de déphasage selon la revendication 2 ou la revendication 3, dans laquelle chaque couche comprend en outre comme élément constituant au moins un élément de lumière (L) sélectionné dans le groupe consistant en hydrogène, oxygène, azote, carbone et halogène.
  5. Ebauche de masque de déphasage selon la revendication 4, dans laquelle chaque couche comprend de l'oxygène ou de l'azote ou les deux.
  6. Ebauche de masque de déphasage selon la revendication 4 ou la revendication 5, dans laquelle le rapport atomique du composant de l'élément de lumière à la somme de silicium, premier et deuxième composants métalliques et composant de l'élément de lumière [L/Si+M1+M2+L)] augmente du côté du substrat vers le côté éloigné.
  7. Ebauche de masque de déphasage selon l'une quelconque des revendications précédentes, dans laquelle le coefficient d'extinction des couches diminue depuis le côté du substrat vers le côté éloigné.
  8. Ebauche de masque de déphasage selon l'une quelconque des revendications précédentes, dans laquelle la conductivité électrique des couches diminue depuis le côté du substrat au côté éloigné.
  9. Ebauche de masque de déphasage selon l'une quelconque des revendications précédentes, où le taux d'attaque avec du gaz à base de fluor des couches augmente depuis le côté du substrat au côté éloigné, et le taux d'attaque avec du gaz à base de chlore des couches diminue depuis le côté du substrat vers le côté éloigné.
  10. Ebauche de masque de déphasage selon l'une quelconque des revendications précédentes, dans laquelle la couche de protection contre la lumière a une épaisseur de 1 à 30 nm, la couche transparente a une épaisseur de 50 à 120 nm et le film entier de déphasage a une épaisseur de 70 à 150 nm.
  11. Ebauche de masque de déphasage selon l'une quelconque des revendications précédentes, dans laquelle le substrat est en quartz.
  12. Masque de déphasage conçu pour un laser excimère KrF, un laser excimère ArF ou une exposition au laser F2, le masque étant obtenu en modelant le film de déphasage dans l'ébauche de masque de déphasage selon l'une quelconque des revendications 1 à 11.
  13. Méthode de transfert de motif comprenant l'exposition d'un photorésist à un motif de lumière à travers le masque de déphasage selon la revendication 12.
EP20070008067 2004-03-31 2005-03-31 Ébauche de masque de déphasage, masque de déphasage, et procédé de transfert de motif Active EP1813983B1 (fr)

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JP2004102388A JP4535240B2 (ja) 2004-03-31 2004-03-31 ハーフトーン型位相シフトマスク用ブランク、ハーフトーン型位相シフトマスク及びパターン転写方法
JP2004102427A JP4535241B2 (ja) 2004-03-31 2004-03-31 ハーフトーン型位相シフトマスク用ブランク、ハーフトーン型位相シフトマスク及びパターン転写方法
JP2004102219A JP4348536B2 (ja) 2004-03-31 2004-03-31 位相シフトマスクブランク、位相シフトマスク及びパターン転写方法
EP20050252030 EP1582920B1 (fr) 2004-03-31 2005-03-31 Ebauche de masque atténué à décalage de phase, masque atténué à décalage de phase, ainsi que procédé pour transférer un motif

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EP20070008068 Active EP1813984B1 (fr) 2004-03-31 2005-03-31 Ébauche de masque de déphasage à tramage, masque de déphasage à tramage, et procédé de transfert de motif
EP20050252030 Active EP1582920B1 (fr) 2004-03-31 2005-03-31 Ebauche de masque atténué à décalage de phase, masque atténué à décalage de phase, ainsi que procédé pour transférer un motif

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EP20050252030 Active EP1582920B1 (fr) 2004-03-31 2005-03-31 Ebauche de masque atténué à décalage de phase, masque atténué à décalage de phase, ainsi que procédé pour transférer un motif

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TWI348590B (en) 2011-09-11
KR20110139174A (ko) 2011-12-28
DE602005025796D1 (de) 2011-02-17
EP1813984A3 (fr) 2007-10-31
EP1813984B1 (fr) 2011-01-05
TW200602803A (en) 2006-01-16
DE602005022096D1 (de) 2010-08-12
KR101165235B1 (ko) 2012-09-13
KR20060045362A (ko) 2006-05-17
KR101165240B1 (ko) 2012-09-13
EP1582920A2 (fr) 2005-10-05
TWI480675B (zh) 2015-04-11
TW201137511A (en) 2011-11-01
EP1582920A3 (fr) 2006-08-09
EP1813984A2 (fr) 2007-08-01
KR101165239B1 (ko) 2012-09-13
TWI480676B (zh) 2015-04-11
EP1813983A2 (fr) 2007-08-01
TW201137510A (en) 2011-11-01
US7556892B2 (en) 2009-07-07
KR20110139175A (ko) 2011-12-28
US20050244722A1 (en) 2005-11-03
KR20110139173A (ko) 2011-12-28
KR101165224B1 (ko) 2012-09-13
DE602005011196D1 (de) 2009-01-08
EP1582920B1 (fr) 2008-11-26

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